Packaging system for preserving perishable items

ABSTRACT

A modified atmosphere package for storing oxygen sensitive goods which contains a gas permeable tray for holding the oxygen-sensitive goods and a gas permeable film wrapped over the tray. The tray is made from foam material; at least about 20 volume percent of said foam material is open cell foam. A hinged flap is connected to a wall of the tray and contains a receptacle in which a source of carbon dioxide (such as dry ice) may be disposed.

CROSS-REFERENCE TO RELATED PATENT APPLICATIONS

This application is a continuation-in-part of applicant's patentapplications U.S. Ser. No. 09/609,798, filed on Jul. 3, 2000, pending,which was a continuation-in-part of U.S. Ser. No. 09/519,105, filed onMar. 6, 2000, U.S. Pat. No. 6,213,294, which was a continuation-in-partof U.S. Ser. No. 09/342,844, filed on Jun. 29, 1999, U.S. Pat. No.6,112,890. This case is also a continuation-in-part of patentapplications U.S. Ser. No. 09/196,450 (filed Nov. 19, 1998), U.S. Pat.No. 6,210,725 and U.S. Ser. No. 09/182,754 (filed Oct. 29, 1998), U.S.Pat. No. 6,023,915.

TECHNICAL FIELD

A packaging system for preserving perishable items which comprises atray made from foam, and a barrier bag enclosing said tray.

BACKGROUND OF THE INVENTION

Applicant's U.S. Pat. No. 6,112,890 describes a packaging system forpreserving perishable items; this patent, and prior art cited in it, arethe most relevant references known to applicant regarding the technologyclaimed in this patent application.

It is an object of this invention to provide an improved packagingsystem for preserving perishable goods.

SUMMARY OF THE INVENTION

In accordance with this invention, there is provided a packaging systemfor preserving a perishable item which comprised of a tray comprised ofopen-cell foam covered with a gas-permeable film, and such tray coveredwith such film is disposed within a sealed, oxygen-impermeable barrierbag consisting of an inert atmosphere containing less than about 0.05volume percent of oxygen. The tray contains a hinged section attached toat least one edge of the tray in which a receptacle is formed for thereceipt of source of carbon dioxide.

BRIEF DESCRIPTION OF THE DRAWINGS

The present invention will be more fully understood by reference to thefollowing detailed description thereof, when read in conjunction withthe attached drawings, wherein like reference numerals refer to likeelements, and wherein:

FIG. 1 is a sectional view of one preferred packaging system of theinvention;

FIGS. 2A, 2B, 2C, 2D, and 2E schematically illustrate one means ofpreparing and using the packaging system of FIG. 1;

FIG. 3 is a sectional view of a portion of the tray used in the systemof FIG. 1;

FIG. 4 is a sectional view of one preferred barrier bag which may beused in the packaging system of FIG. 1;

FIG. 5 is a graph illustrating the oxygen concentrations in a specifiedpackaging material over time with two systems, one of which uses aconventional foam tray, and the other of which uses the open-cell foamtray of this invention;

FIG. 6 is a sectional view of another preferred packaging system of theinvention;

FIG. 7 illustrates a process for making a packaging system in which thebarrier bag expands during the process;

FIG. 8 illustrates a process for limiting the extent to which thebarrier bag can expand during the process;

FIG. 9 is a graph illustrating how the use of granulated carbon dioxideaffects the preferred process;

FIG. 10 is schematic representation of one preferred packaging system ofthis invention;

FIG. 11 is a sectional view of the system of FIG. 10;

FIG. 12 is a sectional view of another preferred tray of the invention;

FIG. 13 is a top view of the tray of FIG. 12;

FIG. 14 is a sectional view of the tray of FIG. 12 after meat has beendisposed in it;

FIG. 15 is a sectional view of the tray of FIG. 12 after meat has beenplaced in it in it and a source of carbon dioxide has been charged intoa receptacle located within a hinged attachment to the tray;

FIG. 16 illustrates the device of FIG. 15, after it has been wrappedwith film and a vent hole has been punched therein;

FIG. 17 illustrates the device of FIG. 16 after it has been placedwithin a barrier bag fitted with a valve and a means for sealing thebag; and

FIG. 18 illustrates a multiplicity of the devices of FIG. 16 disposedwithin a master barrier bag outfitted with a valve and sealing means.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

This specification contains two separate sections. In section one of thespecification, the embodiments of FIGS. 1-9 are described. In sectiontwo of this specification, the embodiment of FIG. 10 is described.

One Preferred Packaging System of the Invention

FIG. 1 is a sectional view of one preferred packaging system 10 which iscomprised of a tray 12 which, in the preferred embodiment depicted,includes flanges 14 around the perimeter of such tray 12. A perishablegood or goods 15 is disposed within tray 12.

The perishable goods which may advantageously be protected by thepackaging system 10 of this invention include oxygen-sensitive food suchas, e.g., red meat (veal, beef, pork, etc.), pasta, cooked food, and thelike. Alternatively, one may preserve perishable non-food items such asphotographic film, computer components, inorganic materials susceptibleto oxidation, etc.

In the preferred embodiment depicted in FIG. 1, a skin layer 19 iscontiguous with and attached to the bottom surface of the tray andpreferably up the side of the tray to the flanges 14.

In the preferred embodiment depicted in FIG. 1, a gas permeable filmmaterial 18, which may include slits or perforations 20, covers theperishable goods 15. This skin layer 19 is illustrated more clearly inFIG. 3.

Referring again to FIG. 1, it will be seen that the tray 12 which isoverwrapped with gas permeable film material 18 is disposed within abarrier bag 22 which surrounds the tray 12 and which preferably is madeof a substantially impermeable material. This barrier bag is attached toa one-way valve 24, which will be described in greater detail elsewherein this specification.

From about 10 to about 150 grams of solid carbon dioxide 16, which maybe in the form a flakes, one or more pellets, an irregular shape, etc.,are disposed outside of tray 12 but within barrier bag 22.

The barrier bag 22, prior to the time it is sealed, contains an opening23.

FIG. 2A is a sectional view of tray 12 attached to skin layer 19. Thetray 12 is comprised of at least 90 weight percent of foam material. Inone preferred embodiment, the foam material is open-cell foam whichcontains at least about 20 volume percent of open cells.

As is known to those skilled in the art, an open-cell cellular plasticis a cellular plastic in which there is a substantial number ofinterconnected cells; see, e.g., A.S.T.M. D883. Reference also made byhad to U.S. Pat. No. 5,798,409 (open cell foams of polystyrene andpolyurethane), U.S. Pat. No. 5,784,845 (open cell foam material madefrom alkenyl aromatic polymer material), U.S. Pat. No. 5,646,193 (rigidopen cell foam material), U.S. Pat. Nos. 5,557,816, 5,475,890, 5,434,024(open cell foam material of polyvinyl chloride, or polyisocyanate, orpolyphenol, or polypropylene), U.S. Pat. Nos. 5,348,587, 5,343,109,5,239,723, 5,139,477 (polyethylene open cell foam material), U.S. Pat.Nos. 4,739,522, 4,395,342 (open cell foam material made from celluloseacetate, or phenol-formaldehyde, or cellular rubber), etc. Thedisclosure of each of these United States patents is hereby incorporatedby reference into this specification.

It is preferred that the open cell foam material be made from a resinselected from the group consisting of polyethylene, polyvinyl chloride,polyacrylonitrile (such as the “BAREX” resin sold by the BritishPetrolem/Amoco company), poly(ethylene terephthalate), polystyrene,rubber-modified polystyrene, ethylenepolystyrene, interpolymers (such as“INDEX” interpolymers sold by Dow Chemical Corporation of MidlandMich.), polypropylene, polyurethane, polyisocyanurate, epoxy, ureaformaldehyde, rubber latex, silicone, fluropolymer or copolymers thereofor blends thereof, and in general any other suitable resin, resinmixture, or any foamable composition which can be made with an open cellstructure such as, e.g., materials made using a silane peroxide catalystsystem (sold by the Sentinel Foam company or Hyanis, Mass.).

As is well known to those skilled in the art, one may vary the degree towhich a foam material contains open-cell structure by the process taughtby applicant in his 1977 article entitled “Controlling the Properties ofExtruded Polystyrene Foam.” This article was presented at theProceedings of the International Conference on Polymer Processing, whichwas held at the Massachusetts Institute of Technology, Cambridge, Mass.,in August 1977. This proceedings were published in 1977 in a book editedby Nam P. Suh and Nak-Ho Sung entitled “Science and Technology ofPolymer Processing” (The MIT Press, Cambridge, Mass., 1977); and adescription of means to control the concentrator of open cells appearedon page 410 of this book. In particular, the correlation between theconcentration of open cells produced in the foam and the melttemperature of the resin/blowing agent mixture used, was discussed.

Referring again to FIG. 2A, the tray 12 is comprised of foam materialwhich contains at least about 20 volume percent of open cells. In onepreferred embodiment, the foam material contains at least about 30volume percent of open cells. It is even more preferred that the foammaterial contain from about 30 to about 90 volume percent of open cellsand, even more preferably, from about 45 to about 90 volume percent ofopen cells. The extent to which a foam material contains open-cell foammay be determined by A.S.T.M. Standard Test D2856-94, “Test Method forOpen-Cell Content of Rigid Cellular Plastics by the Air Pycnometer.”

The open-cells in the foam contain a gas phase with gases which aresubstantially identical to the gases in ambient air. Thus, theopen-cells generally contain a gas phase comprised of from about 19 toabout 22 volume percent of oxygen (depending upon the altitude) and fromabout 78 to about 81 volume percent of nitrogen. In general, such gasphase contains from about 20.5 to about 21 volume percent of oxygen andfrom about 79 to about 79.5 volume percent of nitrogen. However, afterthe open-cells in the gas tray have been treated by the process of thisinvention, they preferably contain less than about 0.05 volume percentof oxygen.

FIGS. 2B, 2C, 2D, and 2E illustrate how use the tray depicted in FIG. 2Acan be used to make the structure depicted in FIG. 1. For the sake ofsimplicity of representation, much of the detailed description of thetray contained in FIG. 2A has been omitted from FIGS. 2B, 2C,2D, and 2E.

After the tray 12 has been fabricated (see FIG. 2A), the good or goods15 are placed in the tray and then wrapped either manually orautomatically with a gas permeable film material 18, or other suitablemeans, to holds the goods 15 in place, thereby forming wrapped tray 30(see FIG. 2C).

The open-cell foam material which comprises tray 12 have as an averagecell diameter of from about 0.0001 to about 0.030 inches and, morepreferably, from about 0.002 to about 0.008 inches. In one preferredembodiment, the cell diameter of such cells is from about 0.003 to about0.007 inches.

The average cell diameter of a foam may be determined in accordance withthe procedure described in applicant's U.S. Pat. Nos. 3,953,739 and4,329,052, the disclosures of which are hereby incorporated by referenceinto this specification. One may also use one or more of the methodsdisclosed in other United States patents, such as, e.g., U.S. Pat. Nos.5,912,729, 5,817,704, 5,810,964, 5,798,065, 5,795,680, 5,790,926,5,786,401, 5,770,634, 5,7532,717, 5,912,729, and the like. Thedisclosure of each of these United States patents is hereby incorporatedby reference into this specification.

Referring again to FIG. 1A, the tray 12 has walls with a thickness 21 offrom about 0.025 to about 0.5 inches and, preferably, from about 0.040to about 0.15 inches. In one embodiment, the thickness 21 is from about0.04 to about 0.1 inches. The thickness of the sidewalls 23 and 25 oftray 12 may be equal to or less than the thickness of the bottom surface27 of tray 12. In one embodiment, the thickness of sidewalls 23 and 25is from 25 to about 50 percent of the thickness of the bottom surface27.

In one preferred embodiment, illustrated in FIG. 2A, the bottom surface27 of tray 12 forms an interior angle (29 or 31) between sidewalls 23 or25 of from about 1 to about 90 degrees and, preferably, from about 25 toabout 50 degrees. Angles 29 and 31 may be the same or different.

Referring again to FIG. 2A, the tray 12 preferably has a density of fromabout 0.1 to about 55 pounds per cubic foot and, preferably from about 1to about 10 pounds per cubic foot, and more preferably from about 1.5 toabout 6 pounds per cubic foot. It is even more preferred that thedensity be from about 2.0 to about 5.0 pounds per cubic foot. In oneembodiment, the density of tray 12 is from about 2 to about 3 pounds percubic foot.

Referring again to FIG. 2A, it will be seen that tray 12 is attached toa skin 19; the means for attaching this skin 19 will be discussedelsewhere in this specification. The thickness of skin 19 is preferablyfrom about 0.0005 to about 0.01 inches and, more preferably, from about0.002 to about 0.005 inches.

In FIGS. 2B through 2E, tray 12 is depicted in various combination withother elements. However, for the sake of simplicity of representation,many of the details of tray 12 depicted in FIG. 2A have been omitted inthese latter Figures.

As is illustrated in FIG. 2B, the perishable goods 15 are placed withintray 12, either manually or automatically. In one embodiment, notillustrated, an absorbent pad is placed between the goods 15 and thebottom of the tray in order to absorb excess juices exuded from thegoods 15.

Referring to FIG. 2C, a gas permeable film material 18 adapted to passboth oxygen and carbon dioxide is wrapped around the entire tray 12. Thefilm material may be adhered to the tray because of its “clingproperties,” and/or it may be heat-treated to cause it to adhere to thetray; in each either event, the film 18 is contiguous with the sides andthe bottom of tray 12 and encloses the perishable goods 15. Thus, as isdisclosed in U.S. Pat. No. 5,698,250, the film 18 may contain additiveswhich allow the film to cling to itself. This film generally has athickness ranging from about 0.5 mil to about 1.5 mils.

These gas-permeable films are well known to those skilled in the art andare described, e.g., in U.S. Pat. Nos. 5,888,597, 5,885,699, 5,852,152(ethylene/vinyl acetate film and ethylene/acrylic acid film), U.S. Pat.Nos. 5,840,807, 5,839,593, 5,804,401, 5,780,085, 5,759,712, 4,056,639,4,011,348, 3,867,558, 3,857,981, 3,728,135, and the like. The disclosureof each of these United States patents is hereby incorporated byreference into this specification.

In one preferred embodiment, film 18 is a polyvinyl chloride filmsupplied by the Borden Packaging and Industrial Products company ofNorth Andover, Mass as “Resinite.” This film 18 has an oxygenpermeability of from about 1100 to about 1400 cubic centimeters per 100square inches per 24 hours, as measured by the Mocori Controls Oxtran100 machine measured at 23 degrees Centigrade. The film has a carbondioxide permeability of from about 12,400 to about 13,4000 cubiccentimeters per 100 square inches per 24 hours as measured by a LindeCell at 23 degrees Centigrade and 1 atmosphere pressure.

In the preferred embodiment depicted in FIG. 2C, film 18 is comprised ofperforations 33, 35, 37, and 39. In this embodiment, it is preferredthat each of such perforations have a maximum cross-sectionaldimensional of less than about 0.05 inches. When such perforations arepresent, it is preferred that from about 1 to about 4 of them occur persquare inch of surface.

Referring to FIG. 2D, the wrapped tray 30 (see FIG. 2C) is wrapped in anoxygen barrier bag 22 which, in the preferred embodiment depicted, ispreferably shaped similarly to a typical bag with an open end into whichto insert the wrapped tray. Such oxygen barrier bags are well known tothose skilled in the art and are described, e.g., in U.S. Pat. Nos.5,862,947, 5,855,626, 5,811,027,5,799,463, 5,798,055, 5,780,085,5,753,182, 5,711,978, 5,700,554, 5,667,827, 5,583,047, 5,573,801,5,573,797, 5,529,833, 5,350,622, 5,346,644, 5,227,255, 5,203,138,5,195,305, 4,857,326, 4,605,175, 4,082,829, 3,953,557, and the like. Thedisclosure of each of these United States patents is hereby incorporatedby reference into this specification.

In one preferred embodiment, the barrier bag described in column 4 ofU.S. Pat. No. 5,698,250 may be used. This bag is commercially availableas product number 325C44-EX861B from the PrintPak, Inc. company ofAtlanta, Ga.

In another preferred embodiment, the barrier bag used is a biaxiallyoriented nylon film coated with an oxygen barrier coating (such aspolyvinylidene chloride) and having a thickness of from about 0.00072 toabout 0.00112 inches. Such a bag is commercially available from theAllied Signal Corporation (of New Jersey) as “Capron Emblem 1530” or“Capron Emblem 2530.”

Regardless of the particular barrier bag used, it is preferred that ithave an oxygen permeability of less than 5 cubic centimeters per 100square inches per 24 hours, as measured by a suitable gas permeabilitymeasuring device, such as the aforementioned Mocon Controls Oxtran 100machine; measurements are taken under ambient conditions. This testmethod is well know, being described in A.S.T.M. Standard Test D-1434“Test Method for Determining Gas Permeability Characteristics of PlasticFilm and Sheeting.” Reference may also be had to U.S. Pat. Nos.5,913,445, 5,882,518, 5,769,262, 5,684,768, and the like. The disclosureof each of these United States patents is hereby incorporated byreference into this specification.

Referring again to FIG. 2D, the barrier bag 22 is preferably operablyconnected to a pressure relief valve 24. The pressure relief valve 24 isadapted to open and allow gas disposed within barrier bag 22 when thepressure within barrier bag 22 is from about 0.05 to about 1.0 poundsper square inch gauge and, more preferably, from about 0.1 to about 0.2pounds per square inch gauge. In an even more preferred embodiment, thevalve 24 is adapted to allow gas disposed within barrier bag 22 to ventto the outside when the pressure within such bag is from about 0.12 toabout 0.14 pounds per square inch gauge.

The valve 24, after it is has opened to vent gas from the barrier bag22, closes when the internal pressure drops within the range of fromabout 0.01 to about 0.04 pounds per square inch gauge.

Pressure sensitive gas valves for releasing gas from a sealed flexiblepouch, such as valve 24, are well known to those skilled in the art.See, for example U.S. Pat. Nos. 5,059,036, 5,419,638, 5,048,846,4,653,661, 4,690,667, and the like. The disclosure of each of theseUnited States patents is hereby incorporated by reference into thisspecification.

In one preferred embodiment, the pressure sensitive gas valve is sold bythe Plitek, Inc. company of 681 Chase Avenue, Elk Grove Village, Ill.60007; see, e.g., a publication by Plitek (entitled “Plitek PressureRelief Valve”) which was published on Jul. 8, 1991. A copy of thispublication is in the file history of U.S. Pat. No. 5,419,638 of Mark D.Jamison.

The valve 24 may be incorporated into the gas barrier bag 24 byconventional means such as, e.g., by means of the “CCL Model 230 ValveApplicator labelling system” which is sold by CCL Industries of 3070Mainway, Units 16-19, Burlington, Ontario L7M3X1. This system is adaptedto be secured to the side of a vertical form-fill and seal machine toapply self-adhesive valve labels to the plastic web on the forming tubesection of the machine just prior to the seal and cut station.

Referring again to FIGS. 2D and 2E. after the sealed tray 30 is disposedwithin the barrier bag 22, solid carbon dioxide 16 is charged into thebarrier bag 22 prior to the time the bag is sealed. In general, fromabout 10 to about 150 grams of solid carbon dioxide is charged tobarrier bag 22. For a description of one use of such solid carbondioxide in a barrier bag without a valve 24, reference may be had toU.S. Pat. Nos. 5,731,023 and 5,737,905. The entire disclosure of each ofthese United States patents is hereby incorporated by reference intothis specification. It should be noted that the amount of solid carbondioxide used in the processes of these patents is substantially lessthan the amount of carbon dioxide generally used in applicant's process.In general, a sufficient amount of carbon dioxide is used to generate atleast about 1.5 liters of gaseous carbon dioxide per kilogram ofperishable goods 15; see, e.g., an article by N. Penney and R. G. Bellentitled “Effect of Residual Oxygen on the Colour, Odour and Taste ofCarbon-Dioxide-Packaged Beef, Lamb and Pork . . . ” published in MeatScience 33 (1993) at pages 245-252.

Referring to FIG. 2E, after the solid carbon dioxide is disposed withinbarrier bag 22, the bag is heat sealed by conventional means; see, e.g.,U.S. Pat. Nos. 5,908,676, 5,799,463, 5,759,653, 5,332,121, and the like.The disclosure of each of these United States patents is herebyincorporated by reference into this specification.

In one embodiment, after the barrier bag 22 has been heat sealed, avacuum is applied through valve 24 to remove air disposed within barrierbag 22.

FIG. 3 is a sectional view, taken through line 3—3 of FIG. 1, of tray12. Referring to FIG. 3, and to the preferred embodiment depictedtherein, it will be seen that tray 12 is comprised of open cell foam 50to which is attached a skin layer 19 which is preferably comprised of amultiplicity of through-holes 52, 54, 56, 58, 60, and 62. These throughholes have a maximum dimension (such as a maximum diameter) of fromabout 5 to about 40 mils and generally extend from the top surface 64 ofthe skin layer 19 to the top surface 66 of the open cell foam layer.

In another embodiment, not shown, no such through holes exist in theskin layer 19. In either embodiment, however, the skin layer has athickness 68 of from about 0.0005 to about 0.01 inches, and, preferably,from about 0.002 to about 0.005 inches.

As will be apparent to those skilled in the art, the structure depictedin FIG. 3 is a laminated structure with one or more skin layers 19and/or 68. Means for producing such a laminated structure are wellknown. Thus, by way of illustration, in the process of Example 4 of U.S.Pat. No. 4,510,031, a 0.2 millimeter thick sheet of anethylene/propylene block copolymer having a density of 0.91 was heatlaminated to both surfaces of a foamed sheet. Thus, by way of furtherillustration, laminates made by bonding a skin layer to a foam core aredescribed in U.S. Pat. Nos. 5,882,776, 5,876,813, 3,633,459, and thelike. Thus, by way of even further illustration, U.S. Pat. No. 4,098,941discloses a process in which a skin layer is formed in situ on a foamcore by heat treatment. The disclosure of each of these United Statespatents is hereby incorporated by reference into this specification.

The skin layers 19 and/or 68 may be adhered to the foam layer 50 byadhesive means, by heat lamination means, by coextrusion, by mechanicalmeans, and by other conventional means known to those skilled in theart. The skin layer 19 and/or the skin layer 68 may consist essentiallyof unfoamed plastic (such as polystyrene, or rubber-modifiedpolystyrene, or polyethylene or polypropylene, mixtures thereof, and thelike), paper, and the like. In another embodiment, the skin layer 19and/or the skin layer 68 may consist essentially of either open cellfoam and/or closed cell foam.

Without wishing to be bound by any particular theory, applicant believesthat the laminated structure possesses substantially more flexuralstrength than the unlaminated foam core and, in many cases, reaches orexceeds the structural strength of an unlaminated closed cell foam core,such as the ones described in U.S. Pat. No. 5,698,250.

Extrusion Process for Making the Foam Tray 12

Processes for making closed cell polystyrene foam are well known tothose skilled in the art. See, e.g., the following United Statespatents, each of which named the applicant as an inventor: U.S. Pat.Nos. 5,356,944, 5,286,429, 4,747,983, 4,329,052, 4,022,858, 3,953,739,3,879,507, and the like. The disclosure of each of these United Statespatents is hereby incorporated by reference into this specification.

Processes for modifying closed-cell polystyrene foam processes to makeopen cell foam are also well known to those skilled in the art. See,e.g., the article by applicant entitled “Controlling the Properties ofExtruded Polystyrene Foam” given at the Proceedings of the InternationalConference on Polymer Processing held at The Massachusetts Institute ofTechnology, Cambridge, Mass. in August of 1977 which was published in abook entitled “Science and Technology of Polymer Processing,” edited byNam P. Suh and Nak-Ho Sung (The MIT Press, Cambridge, Mass, 1977).Reference may also be had to U.S. Pat. Nos. 5,798,409, 5,784,845,5,646,193, 5,557,896, 5,475,890, 5,434,024, 5,343,109, 5,239,723,5,139,477, 4,739,522, 4,395,342, 4,259,373, 4,108,600, 4,107,876,4,082,678, 4,079,170, 3,868,716, 3,844,286, 3,589,592, and the like. Thedisclosure of each of these United States patents is hereby incorporatedby reference into this specification.

As is disclosed in these patents, the conventional process for makingpolystyrene foam, which is described in the aforementioned patents, usesthe well documented extrusion process for producing cellular polystyrenefoam in which a solution of a volatile blowing agent in molten polymer,formed in an extruder under pressure, is forced through an orifice intoan ambient environment of temperature and pressure. The polymersimultaneously expands and cools under conditions that give it enoughstrength to maintain dimensional stability at the time corresponding tooptimum expansion. Stabilization is due to cooling of the polymer phaseto a temperature below its glass transition or melting point. Cooling iseffected by vaporization of the blowing agent, gas expansion, and heatloss to the environment.

The polystyrene foam sheet thus produced is allowed to equilibrate withatmospheric gases for a period of from about 1 to about 5 days, at whichtime it is heat shaped into a container using conventional thermoformingequipment.

FIG. 4 is a schematic view of another system for preserving perishablegoods in which a two compartment barrier bag comprised of compartment102 and compartment 104 communicate with each other via an orifice 106.A chunk of solid carbon dioxide 108 gradually sublimes causing gas totravel via arrows 110 and 112 and, when pressure has built up, to ventthrough valve 24. The system of this FIG. 4 is very similar to thesystem depicted in FIG. 1, with the exception that it utilizes atwo-compartment banier bag rather than a single compartment barrier bag.

FIG. 5 is a graph presenting data generated from the experiments of theExamples described in applicant's copending patent application Ser. No.09/342,844.

Another Preferred Packaging System of the Invention

FIG. 6 shows an packaging system 11 which is substantially identical tothe packaging system 10 depicted in FIG. 1 but which differs frompackaging system 10 in that it contains oxygen absorber 200.

One may use any of the commercially available oxygen absorbers as oxygenabsorber 200. One preferred oxygen absorber 200 is an iron-based oxygenabsorber such as, e.g., the ironbased absorbent described in U.S. Pat.No. 5,928,960. The entire disclosure of this United States patent ishereby incorporated by reference into this specification.

Further reference may be had to U.S. Pat. No. 5,262,375, which alsodiscusses oxygen absorber packets. The entire disclosure of this patentis hereby incorporated by reference into this specification.

One oxygen absorber packet which may be used in the process of thisinvention is manufactured by Multiform Dessicants Incorporated of NorthTonawanda, New York. It is believed that this absorber packet containsiron and silica gel.

Other iron-based oxygen absorbers also will work well as oxygen absorber200.

Referring again to FIG. 6, and in the preferred embodiment depictedtherein, the solid carbon dioxide 16 preferably is in particulate formand has a particle size distribution such that at least about 90 weightpercent of its particles are sized in the range from about 25 microns toabout 1,000 microns and, more preferably, are sized in the range of fromabout 100 to about 500 microns. In one embodiment, at least about 90weight percent of the carbon dioxide particles are in the range of from200 to about 400 microns.

In the embodiment depicted in FIG. 6, it is preferred that the barrierbag 22 have an oxygen permeability of less than 10 cubic centimeters per100 square inches per 24 hours, as measured by suitable gas permeabilitymeasuring device.

Referring again to FIG. 6, and in the preferred embodiment depictedtherein, the tray 12 preferably has a water absorbency of from about 5to about 500 percent. In the test used to determine water absorbency, atray is weighed under ambient conditions and then immersed in water fora period of thirty minutes. Thereafter, the tray is removed from thewater bath and weighed. The ratio of the weight of the “wet tray” tothat of the “dry tray” is at least about 2.0/1.0 and, preferably, atleast 2.5/1.0. A tray with the desired characteristics is commerciallyavailable form Vitembal S. A. of Remoulins, France, as the “Integral”absorbent tray.

A Process of Limiting the Expansion the Barrier Bag

FIG. 7 illustrates the condition of packaging system 11 (see FIG. 6)after the carbon dioxide 16 has sublimated and is released through valve24. Certain components of packaging system 11 have been omitted fromFIG. 7 for the sake of simplicity of representation.

Referring to FIG. 7, it will be seen that barrier bag 22 has a height202 which is substantially greater than the height of the barrier bag 22depicted in FIG. 6. As will be apparent to those skilled in the art,this occurs because the sublimation of the solid carbon dioxide producesa gaseous phase which increases the pressure within barrier bag 22. Someof this pressure is vented to atmosphere via valve 24, but some of thepressure causes barrier bag 22 to increase in volume. If the expansionof barrier bag 22 is unrestrained, and depending upon the concentrationof the solid carbon dioxide 16, the volume enclosed by barrier bag 22could increase by as much as 1,500 percent.

When the packaging system 11 has a large volume, it is difficult to shipefficiently and is more cumbersome to use.

FIG. 8 illustrates a process for limiting the increase in volume of thebarrier bag 22. Referring to FIG. 8, it will be seen that the solidcarbon dioxide 16 within barrier bag 22 causes sublimate to flow in thedirection of arrow 204 through valve 24. It also causes the barrier bag22 to expand in volume, but such volume expansion is limited by thepresence of constraint 206. In the particular embodiment depicted,constraint 206 is comprised of opposing walls 208 and 210 which areseparated by distance 202. An orifice 212 disposed within wall 208 isadapted to receive valve 24 and to allow gas passing through valve 24 toexit the constraint 206. Depending upon the extent of distance 202, theextent to which the barrier bag 22 will be allowed to expand duringsublimation of the solid carbon dioxide 16 can be controlled.

One may use any suitable means for controlling the expansion of thevolume within barrier bag 22. In one embodiment, not shown, wall 208 ishingeably attached at point 214 to wall 209 and may be rotated upwardlyin the direction of arrow 216 and/or downwardly in the direction ofarrow 218, thereby varying the effective distance 202 between wall 208and wall 210 at various points along such wall. Other suitable means forcontrolling the expansion of the volume within barrier bag 22 will beapparent to those skilled in the art.

In one embodiment, the restraining means is comprised of shrink filmwhich is used as the barrier bag 22 (see, e.g., FIG. 1). This shrinkfilm barrier bag 22 is preferably oxygen-impermeable. Some suitableoxygen-impermeable shrink films are described, e.g., in U.S. Pat. Nos.5,645,788, 5,482,770, 5,376,394, 5,302,402, 5,035,8512, 4,894,107, andthe like. The disclosure of each of these United States patents ishereby incorporated by reference into this specification.

As will be apparent, once the shrink film barrier bags 22 are heattreated, they resist deformation by gas pressure, thereby effectivelyreducing the volume of the system and restraining expansion of thepackage.

Referring again to FIG. 8, and in the preferred embodiment depictedtherein, the packaging device 11 constrained by constraint 206 isdisposed within a vacuum chamber 300 comprised of a port 302. Sublimateexiting constraint 206 through valve 24 then can exit vacuum chamber 300through valve 304 in the direction of arrow 306.

As will be apparent to those skilled in the art, the presence of avacuum within vacuum chamber 300 facilitates the removal of oxygen frombarrier bag 22. It is preferred that the vacuum within vacuum chamber300 be less than 10.0 millimeters of mercury absolute. This will causethe pressure within barrier bag to be less than about 10.0 millimetersof mercury absolute.

FIG. 9 is a graph presenting data from an experiment in which variousprocessing parameters were varied. Utilizing a setup such as thatdisclosed in FIG. 2E, an experiment was conducted in which 53 grams ofsolid carbon dioxide, in the form of a block, were disposed within abarrier bag 22 with an internal volume of 250 cubic centimeters, and thebag was thereafter immediately heat sealed to isolate its interiorvolume from ambient conditions. Sublimate was then allowed to escapethrough valve 24, and measurements were taken of the oxygenconcentration within the barrier bag 22 at various points in time. Thissystem took 60 minutes to reach an oxygen concentration as low as 500parts per million.

The experiment described above was repeated, with the exception that 50grams of carbon dioxide in particulate form was substituted for the 53grams of carbon dioxide in block form. The particulate carbon dioxidehad a particle size distribution such that at least 95 percent of itsparticles were within the range of 25 microns to 1,000 microns. Usingthese conditions, the system took only about 27 minutes to reach anoxygen concentration as low as 500 parts per million.

The experiment described above which used particulate carbon dioxide wassubstantially repeated, but only 49.2 grams of particulate carbondioxide were used. Furthermore, instead of immediately sealing barrierbag 22 after charging the particulate carbon dioxide to it, the barrierbag was sealed five (5.0) minutes after the carbon dioxide was charged.Using these conditions, the system took only about 7 minutes to reach anoxygen concentration as low as 500 parts per million.

Thus, it is apparent that, by using particulate carbon dioxide, and bynot sealing the barrier bag 22 immediately after charging such carbondioxide, the efficiency of the system can be increased by at least about600 percent. Furthermore, it is advantageous, when using this improvedprocess, to also utilize one or more of the improvements described inFIG. 8.

Section Two: Another Packaging System of the Invention

FIG. 10 is a sectional view of a preferred packaging system 400 which issimilar to the packaging system 10 of FIG. 1, containing the identicalelements 12, 14, 15, 18, 20 and 23. However, the the cross-sectionalstructure 402 differs. This cross-sectional structure is illustrated inFIG. 11.

Referring to FIG. 11, cross-sectional structure 402 is similar to thecross-sectional structure depicted in FIG. 3 with the exception thatskin layer 68 is disposed on the bottom of structure 402; in thestructure of FIG. 3, by comparison, skin layer 19 is disposed on thetop. Thus, as will be apparent, the tray of the assembly 400 preferablyhas its skin layer at the bottom of such tray.

Referring again to FIG. 11, the laminated structure therein preferablycomprises two layers, layers 50 and 68. The holes 52, 54, 56, 58, 60,and 62 are disposed within layer 50; and the 66 denotes the top surfaceof open cell foam layer 50.

Applicant has discovered that the structure depicted in FIGS. 10 and 11is substantially superior to the structure depicted in FIG. 1 in itsperformance characteristics.

In one embodiment, not shown, the structure depicted in FIGS. 10 and 11is modified so that another skin layer 68 appears on top of loam layer50, thereby forming a three-layer laminated structure.

Referring again to FIG. 10, and in the preferred embodiment depictedtherein, it will be noted that valve 24 and no solid carbon dioxide 16(see FIG. 1) are required in this embodiment. Instead, a vaccum isapplied in the direction of arrow 404 through opening 23 by vacuum means406 (such as vacuum pump 406) connected to opening 23 by line 408.

In the embodiment depicted in FIG. 10), the assembly 400 is preferablydisposed within a chamber 410 comprised of port 412 adapted for theintroduction of packaging gas 414) into the chamber 410.

It is preferred to apply a vacuum to orifice 23 until all of the ambientair is withdrawn both from chamber 410 and assembly 400. It is preferredto remove all of the oxygen from the interstices of tray 12. Althoughthe conditions will vary from tray to tray, and chamber to chamber, ingeneral one may apply a vacuum of from about less than about 1millimeter mercury until the oxygen content within tray 12 is less thanabout 0.05 volume percent.

Once vacuum pump 406 has evacuated substantially all of the oxygen fromassembly 400, inert gas may be introduced via port 412. One may usecarbon dioxide, mixtures of carbon dioxide and nitrogen, pure nitrogen,and other inert gases well known to those skilled in the art. It ispreferred to use carbon dioxide in that it tends to inhibit the growthof bacteria.

Once the assembly 400 has had substantially all of its oxygen removedfrom it, barrier bag 22 may be sealed at opening 23 by closure 416. Anysuitable closure may be used. Alternatively, or additionally, barrierbag 22 may be sealed by heat sealing means.

In the embodiment depicted in FIG. 1, only one tray assembly is showndisposed within the barrier bag 22. In another embodiment, not shown,two or more tray assemblies are disposed within the barrier bag.

In one embodiment, and referring to FIG. 10, the tray 12 is comprised ofa material which, in use, generates chlorine dioxide. In one aspect ofthis embodiment, the tray is comprised of from about 0.01 to about 25weight percent of a water-soluble metal chlorite.

As is known to those skilled in the art, when metal chlorite is in thepresence of water and acid, it produces chlorine dioxide, which is anF.D.A. approved disinfectant. See, e.g., U.S. Pat. Nos. 5,389,390,5,364,650, 5,234,703, 4,362,753, 4,244,978, 4,021,585, and the like. Theentire disclosure of each of these patents is hereby incorporated byreference into this specification.

One may incorporate metal chlorite into the tray by conventional means.Thus, e.g., an aqueous solution of sodium chlorite, e.g., at aconcentration of from about 0.01 to about 20 weight percent, may beapplied to the tray 12, which will absorb it.

In one embodiment, the tray 12 is comprised of from about 0.5 to about25 weight percent of an anionic surfactant such as, e.g., “HOSTAPUR”surfactant sold by the Hoechst Chemical Corporation. “HOSTAPUR” is thesodium salt of an alkane sulfonic acid. Other suitable ionic surfactantswhich promote water absorption in the tray 12 also may be used.

When the tray 12 with comprising the water-soluble metal chlorite iscontacted with both carbon dioxide (form the atmosphere) and water (fromthe goods 15 disposed within the package), a mild acid (carbonic acid)will be formed which will faciliate the formation of chlorine dioxidefrom the metal chlorite.

In another embodiment, not shown, solid metal chlorite is incorporatedas tab on tray 12, or within a sachet on tray 12, or by similar means.

The tray 12, and the assembly 400, have been shown for use in preservingperishable items, such as meat. However, these devices have other uses.Thus, for example, they may be used for maintaining medical items in abacteria-free state, for maintaining electronic equipment in anoxidation-free state, etc.

A Tray with a Hinged Attachment

FIG. 12 is a side sectional view of a tray 500 which contains a hingedattachment 502 comprised of a receptacle 504 for receipt of a source ofcarbon dioxide (not shown). In the embodiment depicted, only one hingedattachment 502 is shown, attached to wall 506 of tray 500. In anotherembodiment, not shown, a second and/or a third and/or a fourth suchhinged attachment is attached to one or more of the other walls of thetray.

The receptacle 504 is adapted to receive a source of carbon dioxide. Bythis term, applicant refers to any material or materials which, underambient conditions, will generate carbon dioxide gas. Thus, by way ofillustration and not limitation, one may use dry ice in various sizesand forms (such as ground powder or pellets), a stoichiometric mixtureof citric acid and sodium bicarbonate, and the like.

Referring again to FIG. 12, and in the preferred embodiment depictedtherein, the receptacle 504 is coated with an adhesive 508 which willtend to retain the source of carbon dioxide within the receptacle 504.Any material may be used which will effect the adhesive purpose withoutinterfering with the conversion of the carbon dioxide source intogaseous carbon dioxide. Thus, by way of illustration, a commerciallyavailable glue may be used as adhesive 508.

Referring again to FIG. 12, particulate matter 510 is shown disposedwithin receptacle 504, and a seal 512 is shown covering receptacle 504and preventing the particulate matter within receptacle 510 fromcontacting the outside atmosphere. When one is ready to pack meat intray 500, one can then remove seal 512 and allow the material in thereceptacle to contact the atmosphere.

Thus, by way of illustration, the particulate matter 510 disposed withinreceptacles 504 may be the aforementioned stoichiometric mixture ofcitric acid and sodium bicarbonate. As is known to those skilled in theart, when this mixture is exposed to moisture, it will react and producegaseous carbon dioxide and sodium citrate, neither of which contaminatefood items.

Thus, by way of further illustration, the particulate matter 510disposed within receptacle 504 may consist of or comprise a material,which upon exposure to moisture, produces chlorine dioxide. Particulatewater-soluble metal chlorite serves this purpose, as is discussedelsewhere in this specification.

Thus, by way of further illustration, the particulate matter 510disposed within receptacle 504 may comprise the iron-based oxygenabsorbing material described elsewhere in this specification.

The hinged attachment 502 is hingably attached to the main body of thetray 500 and, in the embodiment depicted, to wall 506. One may use anymeans of making such hinged attachment. Thus, e.g., wall 506 and hingedattachment 502 may be integrally connected to each other and hingablymoved vis-a-vis each other due to the natural resiliency of tray 500 andthe material from which it is made. Thus, e.g. a receptacle (not shown),such as a plastic or paper pouch, can be adhesively attached to one wallof the tray, and/or attached to such wall by other attachment means.

One preferred means of making such a hingable connection is illustratedin FIG. 12. Referring to FIG. 12, it will be seen that a stress-reliefindentation 514 is cut, formed, or compressed within the lower wall 516of the attachment 502. As will be apparent to those skilled in the art,when force is applied to attachment 502 in the direction of arrow 518,the attachment 502 will tend to pivot downwardly towards wall 506. FIG.16 illustrates the position of attachment 502 after force has beenapplied in the direction of arrow 518.

In one embodiment, the tray depicted in FIG. 12 is substantiallyidentical to the open-cell foam tray 12 described elsewhere in thisspecification. In this embodiment, at least about 20 volume percent ofthe foam material in the tray is open cell foam comprised of amultiplicity of open cells with an average cell diameter of from about0.001 to about 0.020 inches.

In another embodiment, the tray depicted in FIG. 12 is comprised ofsolid, non-porous, unfoamed plastic or thermoplastic material, or metal(such as aluminum). Thus, such tray may be made from polypropylene,polystyrene, polyethylene, polyvinylchloride, polyester, and the like.

The solid trays will typically have a porosity of less than about 5percent and, thus, is not capable of absorbing sufficient quantities ofwater. Thus, when a perishable item such as meat is placed into such asolid tray, liquid exuding from the meat will collect in the bottom ofthe tray, thereby producing an aesthetically displeasing package.

One means of avoiding this problem is illustrated in FIG. 12. As isillustrated in the embodiment depicted in FIG. 12, a layer 501 of theabsorbent open-cell foam material may be adhesively attached to thebottom interior wall 503 of tray 500. This absorbent open-cell foammaterial may have the same properties, or properties similar to, theopen-cell foam material described elsewhere in this specification.

In one embodiment, the layer 501 is disposed but not adhered to thebottom interior wall 503 of tray 500.

FIG. 13 is a top view of the tray of FIG. 12 from which unnecessarydetail has been omitted for the sake of simplicity of representation.

FIG. 14 is a sectional view of the tray of FIG. 12 from whichunnecessary detail has been omitted for the sake of simplicity ofrepresentation. As illustrated in FIG. 14, in the first step of theprocess of this invention a perishable item 520 is placed within thetray 500, preferably substantially in the center of the tray. Thelocation of the perishable item within the tray 500 is not critical. Inone embodiment, perishable item 520 is fresh meat.

As is depicted in FIG. 15, in the next step of the process a source ofcarbon dioxide 522 is then placed within receptacle 504. It is preferredto charge the carbon dioxide source to receptacle 504 within no morethan 60 minutes after the perishable item 520 is placed in the tray 500.

Referring to FIG. 16, the assembly depicted in FIG. 15 is thenoverwrapped with a film 18, which film is described elsewhere in thisspecification. Thereafter, a hole 524 is punched through the film 18 andthe tray 500.

In the configuration depicted in FIG. 16, carbon dioxide from carbondioxide source 522 is free to travel in the direction of arrows 526,528, 528. Thus, e.g., when the source of carbon dioxide is dry ice, suchdry ice will sublimate and cause the carbon dioxide to flow through thesystem and out of orifice, thereby also purging the system of oxygencontained therein.

In the configuration depicted in FIG. 17, the assembly depicted in FIG.16 is disposed within a barrier bag 22 comprised of a valve 24. This newassembly can be evacuated and back-flushed with carbon dioxide, and/ormixtures of carbon dioxide and nitrogen. Alternatively, or additionally,the bag can be sealed after a second source of carbon dioxide 534 isplaced within the barrier bag but outside of the sealed tray assembly.In addition to the second source of carbon dioxide 534, one may alsodispose an oxygen-absorbing agent 200 within the barrier bag but outsideof the sealed tray assembly.

In the embodiment depicted in FIG. 17, one overwrapped tray assembly 535is disposed within a barrier bag 22. In the embodiment depicted in FIG.18, a multiplicity of overwrapped tray assemblies 535 are disposedwithin a master barrier bag 18.

It is to be understood that the aforementioned description isillustrative only and that changes can be made in the apparatus, in theingredients and their proportions, and in the sequence of combinationsand process steps, as well as in other aspects of the inventiondiscussed herein, without departing from the scope of the invention asdefined in the following claims.

Thus, in one embodiment, and referring to FIG. 12, adhesive layer 508may be replaced with a metallized or metal-containing layer 508 whichwill readily be heated up to high temperatures either by microwavesand/or sonic waves and/or light. Thereafter, if a mixture of sodiumbicarbonate and citric acid is disposed within receptacle 504, and/ormicrowave and/or sonic energy and/or light energy is selectivelydirected towards receptacle 504, the layer 508 will heat up and willmelt the mixture of sodium bicarbonate and citric acid, thereby causingit to produce carbon dioxide. Other selective means of preferentiallydirecting energy to the mixture of sodium bicarbonate and citric acidalso may be used.

Thus, in another embodiment, a second hinged assembly 502 is utilizedwhich contains material(s) which will generate oxygen upon exposure tocertain specified conditions and which can be used when it is desired to“bloom” the meat product in the tray prior to sale. Thus, e.g., thesecond receptacle 504 may contain two or more compartments which containmaterials which, when combined, will generate oxygen.

I claim:
 1. A modified atmosphere package for storing oxygen sensitivegoods, comprising a gas permeable tray for holding the oxygen-sensitivegoods, a gas permeable film positioned over and adjacent to said trayforming a first wrapped tray, a barrier bag with an inside surface andan outside surface within which said first wrapped tray is disposed, anda pressure relief valve located on said outside surface of said barrierbag, wherein: (a) said gas permeable tray is comprised of foam material,wherein at least about 20 volume percent of said foam material is opencell foam comprised of a multiplicity of open cells, said open cellscomprise a gas phase which comprise from about 19 to about 22 volumepercent of oxygen and from about 78 to about 81 volume percent ofnitrogen, and said open cells have an average cell diameter of fromabout 0.001 to about 0.020 inches, (b) said gas permeable tray iscomprised of a bottom wall and at least one side wall integrallyconnected to said bottom wall and extending upwardly and outwardly fromsaid bottom wall at an angle of from about 10 to about 85 degrees,wherein each of said bottom wall and said side wall have a thickness offrom about 0.025 to about 0.35 inches, (c) said gas permeable tray has adensity of from about 0.5 to about 15 pounds per cubic foot, (d) a filmof gas permeable material is disposed over and contiguous with saidbottom wall of said gas permeable tray, (e) said barrier bag has anoxygen permeability of less than 5 cubic centimeters per 100 squareinches per 24 hours, and (f) said tray is comprised of a first wall anda first hinged flap integrally connected to said first wall of saidtray, wherein said first hinged flap is comprised of a first receptacle.2. The modified atmosphere package as recited in claim 1, wherein asource of carbon dioxide is disposed within said first receptacle. 3.The modified atmosphere package as recited in claim 1, wherein saidfirst receptacle is comprised of an arcuate section with an inner curvedwall and an outer curved wall.
 4. The modified atmosphere package asrecited in claim 3, wherein a coating of adhesive material is disposedon said inner curved wall.
 5. The modified atmosphere package as recitedin claim 2, wherein a source of chlorine dioxide is disposed within saidfirst receptacle.
 6. The modified atmosphere package as recited in claim2, wherein an oxygen-absorbing material is disposed within said firstreceptacle.
 7. The modified atmosphere package as recited in claim 1,wherein said first hinged flap is comprised of first means for sealingsaid receptacle.
 8. The modified atmosphere package as recited in claim1, wherein said tray is comprised of a second wall and a second hingedflap integrally connected to said second wall of said tray, wherein saidsecond hinged flap is comprised of a second receptacle.
 9. The modifiedatmosphere package as recited in claim 8, wherein said second receptacleis comprised of a source of oxygen.
 10. The modified atmosphere packageas recited in claim 1, wherein from about 2 to about 25 wrapped traysare disposed within said barrier bag, wherein each of said wrapped traysis produced by a process in which a gas permeable film is positionedover and adjacent to a gas permeable tray, and wherein: (a) said gaspermeable tray is comprised of foam material, wherein at least about 20volume percent of said foam material is open cell foam comprised of amultiplicity of open cells, said open cells comprise a gas phase whichcomprise from about 19 to about 22 volume percent of oxygen and fromabout 78 to about 81 volume percent of nitrogen, and said open cellshave an average cell diameter of from about 0.001 to about 0.020 inches,(b) said gas permeable tray is comprised of a bottom wall and at leastone side wall integrally connected to said bottom wall and extendingupwardly and outwardly from said bottom wall at an angle of from about10 to about 85 degrees, wherein each of said bottom wall and said sidewall have a thickness of from about 0.025 to about 0.35 inches, (c) saidgas permeable tray has a density of from about 0.5 to about 15 poundsper cubic foot, (d) a film of gas permeable material is disposed overand contiguous with said bottom wall of said gas permeable tray, and (e)said tray is comprised of a first wall and a first hinged flapintegrally connected to said first wall of said tray, wherein said firsthinged flap is comprised of a first receptacle.
 11. The modifiedatmosphere package as recited in claim 1, wherein a source of carbondioxide is disposed within said barrier bag but outside of said firstwrapped tray.
 12. The modified atmosphere package as recited in claim 1,wherein a source of carbon dioxide is disposed within said barrier bag.13. The modified atmosphere package as recited in claim 10, wherein asource of carbon dioxide is disposed within said barrier bag but outsideof each of said wrapped trays.
 14. The modified atmosphere package asrecited in claim 10, wherein a source of carbon dioxide is disposedwithin said barrier bag.